CN101372457A - A kind of preparation method of alkyl trimethyl quaternary ammonium salt - Google Patents

Abstract

A method for preparing alkyl trimethyl quaternary ammonium salt belongs to the technical field of organic compound synthesis. In the preparation method, methyl carbonate is taken as a quaternizing reagent to synthesize monomethyl-carbonate quaternary ammonium salt, and the quaternary ammonium salt with other counter ions is synthesized by hydrolysis reaction or displacement reaction with various acids (alkalis). The preparation method has the advantages of no environmental pollution or toxin residue, and the product prepared by the method is widely applied to the field of daily chemicals and other industrial fields.

Description

A kind of preparation method of alkyl trimethyl quaternary ammonium salt

technical field

The invention relates to a preparation method for synthesizing alkyl trimethyl quaternary ammonium salts with novel counter ions using dimethyl carbonate as a quaternizing agent.

Background technique

The traditional synthesis methods of alkyl trimethyl quaternary ammonium salts mostly use methyl chloride, methyl bromide, dimethyl sulfate, etc. as quaternizing reagents. These traditional quaternizing reagents have certain toxicity and corrosiveness, and the reaction process consumes a large amount , there is a serious environmental pollution problem, and the products prepared with these quaternization reagents will have a certain degree of toxic residue, which will cause certain harm to the human body when used in daily chemicals.

As a new type of green organic chemical raw material, dimethyl carbonate can replace traditional methylation reagents such as dimethyl sulfate, methyl chloride, and methyl bromide, and can undergo methylation reactions on atoms such as carbon, nitrogen, sulfur, and oxygen. However, in the synthesis of quaternary ammonium salt compounds, dimethyl carbonate is used as a quaternizing agent to react with alkyldimethyl tertiary amines, and there are few reports in the literature.

Contents of the invention

The purpose of the present invention is to overcome the deficiencies of traditional synthetic methods to environmental pollution and residual toxicity of products, to provide a kind of nontoxic synthetic monomethyl carbonate quaternary ammonium salt with dimethyl carbonate as quaternization reagent, and to use this as raw material to synthesize The preparation method of the alkyl trimethyl quaternary ammonium salt of other counter ions.

The chemical structural formula of alkyl trimethyl quaternary ammonium salt of the present invention is as follows:

In the formula: R is a saturated, unsaturated, linear or branched alkyl group of C ₁ to C ₂₂ ;

A ^- is CH ₃ CO ₃ ^- , HCO ₃ ^- , HCOO ^- , CH ₃ COO ^- , lactate, laurate, myristate, octadecanoate, HSO ₄ ^- , NO ₃ ^- , H ₂ PO ₄ ^- , OH ^- .

The synthetic method of the present invention is to utilize dimethyl carbonate to react with alkyl dimethyl tertiary amine as quaternizing agent to generate monomethyl carbonate quaternary ammonium salt, and monomethyl carbonate quaternary ammonium salt is hydrolyzed to generate bicarbonate quaternary ammonium salt Salt, monomethyl carbonate quaternary ammonium salt reacts with various organic acids, inorganic acids or bases to form quaternary ammonium salts with other counter ions.

The synthesis of the monomethyl carbonate quaternary ammonium salt takes alkyl dimethyl tertiary amine and dimethyl carbonate as raw materials to react in a reactor, and the molar ratio of tertiary amine to dimethyl carbonate is 1:1～1 :5, reaction temperature 80～200 ℃, reaction time 1～10h. The synthetic reaction formula is as follows:

The synthesis of the bicarbonate quaternary ammonium salt is a hydrolysis reaction of monomethyl carbonate quaternary ammonium salt, the molar ratio of monomethyl carbonate quaternary ammonium salt to water is 1:1～1:10, and the reaction temperature is 20～90°C , Reaction time 1 ~ 7h. The synthetic reaction formula is as follows:

The synthesis of other described counterion quaternary ammonium salts is that monomethyl carbonate quaternary ammonium salt reacts with various organic acids, inorganic acids and alkalis in methanol solvent, and the mol ratio of monomethyl carbonate quaternary ammonium salt and acid (alkali) The ratio is 1:0.6~1:2, the reaction temperature is 10~60°C, and the reaction time is 2~7h. The synthetic reaction formula is as follows:

The quaternary ammonium salt surfactant with novel counterion synthesized by the present invention has better surface activity than traditional surfactants; the synthetic method of the present invention has adopted the green chemical raw material dimethyl carbonate, which avoids the residue of toxic raw materials in the product, It reduces the toxicity of the product to the human body and the pollution to the environment.

Detailed ways

The present invention will be described below in conjunction with the embodiments.

Example 1

Weigh 21g of dodecyldimethyl tertiary amine and 18g of dimethyl carbonate, add them into a 100mL reaction kettle, slowly raise the temperature to 105°C, and stir for 2h. After the reaction was completed, it was naturally cooled to room temperature, and the product was collected and recrystallized to obtain ammonium dodecyltrimethylammonium carbonate as a white solid. Weigh 3 g of ammonium dodecyl trimethyl methyl carbonate and 10 g of water, add them into a 50 mL flask, and stir at 30°C for 5 h. After the reaction was completed, it was concentrated and recrystallized to obtain a white solid of dodecyltrimethylammonium bicarbonate.

Example 2

Weigh 12g of octadecyldimethyl tertiary amine and 16g of dimethyl carbonate, add them into a 500mL reaction kettle, slowly raise the temperature to 110°C, and stir for 3h. After the reaction was completed, it was naturally cooled to room temperature, and the product was collected and recrystallized to obtain octadecyl trimethyl ammonium methyl carbonate as a white solid. Weigh 4g of ammonium octadecyltrimethylmethyl carbonate and 9g of water into a 50mL flask, and stir at 30°C for 5h. After the reaction was completed, it was concentrated and recrystallized to obtain a white solid of octadecyltrimethylammonium bicarbonate.

Example 3

Weigh 15g of dodecyldimethyl tertiary amine and 16g of dimethyl carbonate, add them into a 100mL reaction kettle, slowly raise the temperature to 105°C, and stir for 2h. After the reaction was completed, it was naturally cooled to room temperature, and the product was collected and recrystallized to obtain ammonium dodecyltrimethylammonium carbonate as a white solid. Weigh 5g of ammonium dodecyltrimethylmethyl carbonate and 1g of acetic acid, add them into a 50mL flask filled with 10mL of methanol, and stir at 35°C for 4h. After the reaction, methanol was distilled off under reduced pressure, and recrystallized to obtain dodecyltrimethylammonium acetate as a white solid.

Example 4

Weigh 16g of tetradecyldimethyl tertiary amine and 15g of dimethyl carbonate, add them into a 100mL reaction kettle, slowly raise the temperature to 110°C, and stir for 3h. After the reaction was completed, it was naturally cooled to room temperature, and the product was collected and recrystallized to obtain tetradecyltrimethylammonium methyl carbonate as a white solid. Weigh 5g of ammonium tetradecyltrimethylmethyl carbonate and 1g of acetic acid, add them into a 50mL flask containing 10mL of methanol, and stir at 35°C for 4h. After the reaction was completed, the methanol was distilled off under reduced pressure, and recrystallized to obtain a white solid of tetradecyltrimethylammonium acetate.

Example 5

Weigh 15g of dodecyldimethyl tertiary amine and 16g of dimethyl carbonate, add them into a 100mL reaction kettle, slowly raise the temperature to 110°C, and stir for 2h. After the reaction was completed, it was naturally cooled to room temperature, and the product was collected and recrystallized to obtain ammonium dodecyltrimethylammonium carbonate as a white solid. Weigh 4 g of ammonium dodecyl trimethyl methyl carbonate and 6 g of lauric acid, add them into a 50 mL flask filled with 18 mL of methanol, and stir at 45°C for 4 h. After the reaction was completed, the methanol was distilled off under reduced pressure, and recrystallized to obtain a white solid of dodecyltrimethylammonium laurate.

Example 6

Weigh 20g of tetradecyldimethyl tertiary amine and 15g of dimethyl carbonate, add them into a 100mL reaction kettle, slowly raise the temperature to 110°C, and stir for 3h. After the reaction was completed, it was naturally cooled to room temperature, and the product was collected and recrystallized to obtain tetradecyltrimethylammonium methyl carbonate as a white solid. Weigh 5g of ammonium tetradecyltrimethylmethyl carbonate and 4.2g of lauric acid, add them into a 50mL flask filled with 10mL of methanol, and stir at 45°C for 4h. After the reaction was completed, the methanol was distilled off under reduced pressure, and recrystallized to obtain tetradecyltrimethylammonium laurate as a white solid.

Claims (9)

1. alkyl trimethyl quaternary ammonium salt is characterized in that chemical structural formula is as follows:

In the formula: R is C ₁～C ₂₂Saturated, unsaturated, straight chain, the alkyl of side chain;

A ^-Be CH ₃CO ₃ ^-, HCO ₃ ^-, HCOO ^-, CH ₃COO ^-, lactate, laurate, cardamom acid group, stearic acid root, HSO ₄ ^-, NO ₃ ^-, H ₂PO ₄ ^-, OH ^-

2. alkyl trimethyl quaternary ammonium salt according to claim 1 is characterized in that: the gegenion of quaternary ammonium salt partly is CH ₃CO ₃ ^-, HCO ₃ ^-, HCOO ^-, CH ₃COO ^-, lactate, laurate, cardamom acid group, stearic acid root, HSO ₄ ^-, NO ₃ ^-, H ₂PO ₄ ^-, OH ^-Deng.

3. alkyl trimethyl quaternary ammonium salt according to claim 1, it is characterized in that: come carbonate synthesis mono-methyl quaternary ammonium salt with methylcarbonate as quaternizing agent, synthesize quaternary ammonium salt by hydrolysis reaction or with various acid (alkali) generation replacement(metathesis)reaction again with other gegenion.

4. the synthetic method of quaternary ammonium salt according to claim 3 is characterized in that: alkyl dimethyl tertiary amide and methylcarbonate generation quaterisation, and carbonate synthesis mono-methyl quaternary ammonium salt, the building-up reactions formula is as follows:

5. the synthetic method of quaternary ammonium salt according to claim 3 is characterized in that: carbonic acid mono-methyl quaternary ammonium salt generation hydrolysis reaction, and synthetic is the quaternary ammonium salt of gegenion with the bicarbonate radical, the building-up reactions formula is as follows:

6. the synthetic method of quaternary ammonium salt according to claim 3, it is characterized in that: carbonic acid mono-methyl quaternary ammonium salt and various organic acid, mineral acid and alkali reaction, synthetic gegenion are HCOO ^-, CH ₃COO ^-, lactate, laurate, cardamom acid group, stearic acid root, HSO ₄ ^-, NO ₃ ^-, H ₂PO ₄ ^-, OH ^-Quaternary ammonium salt, the building-up reactions formula is as follows:

7. the synthetic method of carbonic acid mono-methyl quaternary ammonium salt according to claim 4 is characterized in that comprising following reaction conditions: the mol ratio of tertiary amine and methylcarbonate is 1:1～1:5,80～200 ℃ of temperature of reaction, reaction times 1～10h.

8. the synthetic method of hydrogen-carbonate quaternary ammonium salt according to claim 5 is characterized in that comprising following reaction conditions: the mol ratio of carbonic acid mono-methyl quaternary ammonium salt and water is 1:1～1:10,20～90 ℃ of temperature of reaction, reaction times 1～7h.

9. the synthetic method with other gegenion quaternary ammonium salts according to claim 6 is characterized in that: react in methanol solvate, carbonic acid mono-methyl quaternary ammonium salt is 1:0.6～1:2 with the mol ratio of acid (alkali), 10～60 ℃ of temperature of reaction, reaction times 2～7h.